Epoxy curing agents, method for making them, method of curing epoxy resins, and cured epoxy resins

ABSTRACT

A new class of epoxy curing agents has been discovered that utilizes the monomer of (a) urea-formaldehyde, (b) phenol modified urea-formaldehyde, or (c) thiourea-formaldehyde as the center of a polyamine molecule. The ether monomers are reacted with conventional aliphatic, cycloaliphatic, and aromatic polyamines to split off alcohol and water-yielding urea-formaldehyde etc., polyamine epoxy curing agents. Epoxy resins can be readily cured and, with some curing agents, under water, giving new cured epoxy resins.

This invention relates to novel compounds useful as epoxy curing agents,to a method for making these new compounds, to a novel method of curingepoxy resins, and to novel cured epoxy resins.

A new class of epoxy curing agents has been discovered that utilizes thestructure of urea-formaldehyde and also the structure of phenol-modifiedurea-formaldehyde as the center of a polyamine molecule. The aminegroups are arranged around the urea-formaldehyde center in a radialfashion.

This may be represented as: ##STR1## where X¹ is ##STR2## and X² iseither identical to X¹ or is ##STR3## R¹, R², R³, and R⁴ are definedbelow.

This structure has a low amount of steric hindrance; that is, thestructure of the molecule allows the most space between its components.This provides easy access for an epoxy molecule to react with thesewidely spaced amine groups.

The structures of these new compounds give a high degree of crosslinking when reacted with epoxy resins and, therefore, contribute to thetoughness and strength of the cured amine-epoxy resin.

Another advantage of incorporation of the urea-formaldehyde structure inthe polyamine curing agent is that the curing agent is water-white incolor, and so the subsequently cured amine-epoxy resin can bewater-white. Urea-formaldehyde resins themselves are intrinsicallycolorless and resist becoming yellowish, and this same resistance toyellowing can be incorporated in the urea-formaldehyde polyaminestructure.

The phenol-modified urea-formaldehyde resins have some yellowness, butare quite light.

Both the urea-formaldehyde polyamines and the phenol-modifiedurea-formaldehyde polyamines can be low in cost, because urea,formaldehyde, and phenol are low-cost raw materials, and so are many ofthe polyamines.

Success in manufacturing these urea-formaldehyde polyamine curing agentsdepends, in part, on employing a process of urea-formaldehyde synthesisthat produces largely monomeric urea-formaldehyde ether molecules.

One successful method of making urea-formaldehyde ether monomers is toreact urea and paraformaldehyde in a low-molecular-weight alcohol, suchas methanol at a ratio of urea molecules to formaldehyde molecules ofone to four. This results in the following general structure: ##STR4##

Here, R is a methyl, ethyl, propyl, or butyl radical.

Once this monomeric urea-formaldehyde ether molecule has beensynthesized, it can be reacted directly with any of a number ofpolyamines including those that are presently utilized in themanufacture of amine curing agents.

A fundamental discovery of this patent is the discovery that polyaminessplit the ether groups of the above urea-formaldehyde molecule. Then,one of the amine groups of the polyamine forms a carbon-nitrogen bond atthe side of the ether splitting, giving off the reaction products ofalcohol and water. For example: ##STR5##

R⁵ is a lower alkyl radical, having one to four carbon atoms.

This ease of splitting of these ether groups is somewhat surprising,because I had earlier found that the corresponding ether groups in amelamine formaldehyde resin are not split, under the same conditions.

As stated above, X¹ may be generalized as ##STR6##

The following table shows the complete grouping of these radicals thatcan be R¹.

    __________________________________________________________________________    CHART FOR R.sup.1                                                             Name of Polyamine                                                             Used to React with                                                            U-F Monomer, etc.     R.sup.1                                                 __________________________________________________________________________    (a)                                                                              diethylene triamine                                                                               ##STR7##                                                 (b)                                                                            triethylene tetramine                                                                             ##STR8##                                                 (c)                                                                            hexamethylene diamine                                                                            CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2        (d)                                                                              polyoxypropylene diamines                                                                        CH(CH.sub.3)CH.sub.2 [OCH.sub.2CH(CH.sub.3)]                                  .sub.X                                                     X = 2.6 has M.W. (molecular weight)                                           of 230 approx.                                                                X = 5.6 has M.W. (molecular weight)                                           of 400 approx.                                                                Commercial Name:                                                              Jeffamine D-230                                                               Jeffamine D-400                                                               Texaco Chemical Co.                                                          (e)                                                                            polyoxypropylene triamine                                                                         ##STR9##                                                  X + Y + Z = 5.3                                                               M.W. of 400                                                                   Commercial Name:                                                              Jeffamine T-403                                                              (f)                                                                            poly(oxyethylene)diamine                                                                          ##STR10##                                                 b = 13.5                                                                      a + c = 3.5                                                                   M.W. of 600                                                                   Commercial Name:                                                              Jeffamine ED diamine                                                         (g)                                                                            trimethyl hexamethylene diamine                                                                   ##STR11##                                                (h)                                                                            Naminoethyl piperazine                                                                            ##STR12##                                                (i)                                                                            1,5 aminomethyl pentane diamine                                                                   ##STR13##                                                (j)                                                                            isophorone diamine                                                                                ##STR14##                                                (k)                                                                            1,2-diamine cyclohexane                                                                           ##STR15##                                                (l)                                                                            xylene diamine                                                                                    ##STR16##                                                (m)                                                                            2,4-Bis(p-amino benzyl)aniline an aromatic polyamine                                              ##STR17##                                                (n)                                                                            mixture of                                                                    BABA (du Pont), mixture principally of methylene dianiline                                        ##STR18##                                                 and                                                                           2,4 bis(p-amino benzyl)aniline                                                                    ##STR19##                                                (o)                                                                            oleyl diamine      CH.sub.2CH.sub.2CH.sub.2                                __________________________________________________________________________

For all of the amines (a) through (n) in the above table, R² and R³ areboth H. For the oleyl diamine, amine (o), either R² or R³, but not both,is C₁₈ H₃₅ and the other one is again H.

In the formula ##STR20## X¹ is as defined above, while X² may either beidentical to X¹ or may be ##STR21## where R⁴ is hydrogen or an alkylradical with one to nine carbon atoms.

There are amine curing agents on the market that are made from phenol,formalin (a water solution of formaldehyde) and a polyamine. These haveno relationship to the urea-formaldehyde polyamines of the presentinvention because they are made by a different chemical route, and havevastly different properties. The manufacture of thesephenol-formaldehyde amines is illustrated by Product Data Sheet22-E-370-2-6 published by Veba-Chemi AG of Germany, which describes thereacting of phenol and 36% formalin using a basic catalyst. Thepolyamine is added to this water solution of the phenol-formaldehyderesin, and subsequently the water is driven off, resulting in a yellowviscous liquid.

As stated earlier, this resin is in no way related to theurea-formaldehyde polyamines of this invention, for no ether groups areformed in the water solution of phenol and formaldehyde under theabove-stated basic conditions.

The urea-formaldehyde ether monomers are made in an alcohol medium. Theurea, paraformaldehyde (a solid form or polymer of formaldehyde havingtypically 91% formaldehyde content), and an alcohol, such as methanol,are first subjected to basic conditions under low heat such as 50° C.This brief alkaline reaction causes the paraformaldehyde to dissolve.Then the reaction is made strongly acidic, e.g., a pH of 2; at this timean exotherm takes place, as a result of the formation of ether groups,for ethers of urea-formaldehyde are only formed under acid conditions.The reaction is held at 70°-80° C. for a time in the order of one hour,to insure good ether formation. The monomer reaction is then finished bybringing the pH to 7.0.

There may be small amounts of methylol groups in these urea-formaldehydemonomers. These methylol groups react with the polyamine in the samemanner as the ethers react. ##STR22##

The formation of ether groups in the urea-formaldehyde resin can befollowed by infrared spectrophotometry analysis. A sample of thereaction is scanned in an infrared spectroscopy instrument. The ethergroups in urea-formaldehyde are shown by an infrared peak at 9.3 microns(1075 cm⁻¹). See the book An Infrared Spectroscopy Atlas for theCoatings Industry, 1980, Federation of Societies for Coating Technology,page 33.

This 9.3 micron peak develops soon after acidic conditions are made. Thefinal urea-formaldehyde ether monomer has a very large 9.3 micron etherpeak at the end of the reaction.

The progress of the reaction of the urea-formaldehyde ether monomer withthe polyamine can be followed by noting that the ether peak is destroyedvery soon after the urea-formaldehyde ether monomer is added to thepolyamine. The finished reaction product has no trace of this 9.3 micronpeak. The mixing of the urea-formaldehyde ether monomer into thepolyamine is generally done at low temperature, such as 25° C. Anexotherm takes place during the mixing which raises the temperature some30° C. Then the alcohol and water of reaction are distilled off givingtypically a water white, low viscosity, transparent liquid withremarkably good epoxy curing properties.

Some specific examples illustrate the formation of the urea-formaldehydeether and related monomers and the reaction of the monomers withpolyamines.

EXAMPLE 1 Urea-Formaldehyde Ether Monomer in Methanol

In a three liter glass flask fitted with a stainless steel paddlestirrer, thermometer, a pH electrode and a reflux condenser, is charged:

1200 g. methyl alcohol 99%

1200 g. 91% flake paraformaldehyde (corresponding to 1092 g. of 100% CH₂O=36.4 moles)

540 g. urea=9 moles.

This mix was stirred and heated to 40° C. The pH of this mix was 3.0.The pH was brought to 10.5 by the addition of a small amount of 40%sodium hydroxide. As the temperature rose to 55° C., theparaformaldehyde and the urea were dissolved, making a clear solution.At this point 50% H₂ SO₄ was added to bring the pH to 2.5. This caused amild exotherm, bringing the temperature to 78° C. The pH was maintainedat 2.0-2.5, and the temperature was maintained at about 80° C. for aboutforty minutes. Then the pH was brought to 7.0 with NaOH. The cooledurea-formaldehyde solution had suspended Na₂ SO₄ in it, which wasfiltered out leaving a water-white, transparent, low-viscosity liquidcontaining about 55% non-volatile urea-formaldehyde ether monomer.Infrared analysis showed a strong peak at 9.3 microns, indicating ethersof methylol groups.

EXAMPLE 2 Thiourea-Formaldehyde Ether Monomer in Methanol

It has been found that thiourea ##STR23## readily reacts in the samemanner as urea in making the monomer.

In a 500 ml. flask fitted with a stainless steel paddle stirrer,thermometer, a pH electrode and reflux condenser, was charged:

One mole, 76 g. thiourea, crystals, 99%

Four moles, 132 g. 91% flake paraformaldehyde (corresponding to 120 g.of 100% CH₂ O) 200 g. methyl alcohol 99%.

This mix was stirred and heated to about 40° C. The pH of this mix was5.2. The pH was brought to 11.1 by the addition of a small amount of 40%sodium hydroxide. As the temperature rose to 60° C., theparaformaldehyde and thiourea dissolved making a clear solution. At thispoint 50% H₂ SO₄ was added to bring the pH to 2.5. This caused a mildexotherm bringing the temperature to 70° C. This mix was stirred for onehour maintaining the temperature at 65° to 70° C.

During this time the pH spontaneously fell to 1.65. Then the pH wasbrought to 7.0 with NaOH. The cooled thiourea-formaldehyde solution hadsuspended Na₂ SO₄ in it, which was filtered out leaving a water-white,transparent low-viscosity liquid containing about 48% non-volatilethiourea-formaldehyde ether monomer.

EXAMPLE 3 Composite Urea-Nonyl-Phenol Formaldehyde Ether Monomer

In a 500 ml. glass flask fitted with a stainless steel paddle stirrer,thermometer, pH electrode, and reflux condenser, the followingingredients were added:

0.5 mole, 110 g. nonyl phenol

0.5 mole, 30 g. urea

3.03 mole, (100 g. of 91% paraformaldehyde corresponding to 91 g. 100%CH₂ O) 250 g. isopropyl alcohol, 99%.

This mix was heated and stirred while 40% NaOH was added to bring the pHfrom 2.5 to 11.0. At 85° C. the paraformaldehyde and urea were dissolvedto make a clear solution. Then 50% H₂ SO₄ was added to bring the pH to1.2. A mile exotherm took place, causing some refluxing. The temperaturewas maintained at about 70° C. for an hour while the pH was held at ornear 1.2. Then NaOH was used to bring the pH to 7.0. The filteredsolution was a light yellow transparent solution containing about 47%urea-nonyl phenol formaldehyde ether monomer. A large infrared peak at9.3 microns indicated ethers of methylol groups.

EXAMPLE 4 Composite Urea-Phenol Formaldehyde Ether Monomer

In a one liter glass flask fitted with a stainless steel paddle stirrer,thermometer, pH electrode and reflux condenser, the followingingredients were added:

300 g. methyl alcohol 99%

2 moles, 188 g. phenol, U.S.P.

1 mole, 60 g. urea

3 moles, 99 g. 91% paraformaldehyde, (corresponding to 90 g. 100% CH₂O).

The mix was stirred and heated while 40% NaOH was added to bring the pHfrom 6.5 to 9.5. At 50° C. the paraformaldehyde dissolved, forming atransparent, slightly yellow liquid. Then 50% H₂ SO₄ was added to bringthe pH to 2.1. An exotherm took place, bringing the temperature from 52°to 68° C. The pH dropped to 1.0. The temperature was maintained at 64°C. for ten minutes and the pH was brought from 1.0 to 7.0 with NaOH.

The cooled solution had some white precipitate which was filtered off,leaving a water-white, transparent solution. Infrared analysis showed astrong urea carbonyl peak at 6.05 microns and a large ether peak at 9.3microns. The solution had about 50% non-volatile urea-phenolformaldehyde ether monomer.

EXAMPLE 5 Urea-Formaldehyde Ether Monomer Reacted with an AromaticPolyamine

The urea-formaldehyde ether monomer of Example 1, in an amount of 85grams (47.5 grams of non-volatiles, i.e., 1 equivalents), is reactedwith 1 mole (304 grams) of du Pont BABA, having a composition, weightpercent:

p,p-methylene dianiline: 3-10%

2,4-bis(p-aminobenzyl) aniline (triamine): 70-80%

tetramine: 10-80%

higher amines: 1.

The aromatic polyamine was heated and stirred in a flask to 100° C. andthe urea-formaldehyde ether monomer was added over 20 min. time and thetemperature had climbed to 125° C.

Then 50 g. of benzyl alcohol was added to reduce the viscosity of thisthick red brown liquid with a whitish crust on top. Methanol wasdistilled off during this time. Subsequently the whitish crust wasdispersed in the red brown liquid and the crust dissolved into the mainliquid giving a transparent viscous liquid at 150° C.

This liquid solidified as a dark red-brown brittle solid at about 90°C., considerably higher than the starting polymethylene dianiline. Therewas a urea carbonyl peak shown in infrared analysis of the final productat about 6.05 microns. This was not present in the startingpolymethylene dianiline. The infrared peak at 6.05 microns indicatedthat a compound had been formed between the polymethylene dianiline andthe urea-formaldehyde ether monomer.

EXAMPLES OF THE REACTION OF THE UREA-FORMALDEHYDE AND RELATED ETHERMONOMERS WITH POLYAMINES

All reactions were done in a glass flask fitted with paddle stirrer,thermometer, addition funnel and a distillation condenser. In all casesthe polyamine was stirred in the flask at room temperature, while theurea-formaldehyde ether or related monomer solution in alcohol was addedto the polyamine. If the opposite addition were done,--i.e., adding thepolyamine to the urea-formaldehyde ether solution--a gel would result ina short time. A substantial exotherm results from the addition of themonomer solution etc. to the polyamine during the ten to twenty minutesaddition time. Slow addition is important, for too-rapid addition canresult in some gel particles.

After the addition of the monomer was complete, alcohol and water weredistilled off from the urea-formaldehyde polyamine or related polyamine.Some distillations were at atmospheric pressure where the residuetemperature was 130° C. Other distillations were done under reducedpressure of about 25 inches of vacuum where the temperature was 75° C.

In the following table urea-formaldehyde ether, is abbreviated to UF,urea-formaldehyde ether monomer to UFM, andurea-phenol-substituted-formaldehyde ether to UPFM.

                                      TABLE 1                                     __________________________________________________________________________                                           Properties of the UF Polyamine         Example                                               Viscosity at                                                                  25° C.           No.  UFM or UPFM    Polyamine          Color of Liquid                                                                              in                      __________________________________________________________________________                                                          Poises                  6    130 g. UFM of Example 1                                                                      155 g. diethylene triamine                                                                       water white    1.2                          = 72 g. non-volatile                                                                         1.5 moles          transparent                                 = 1.5 equivalents                                                        7    260 g. UFM of Example 1                                                                      206 g. diethylene triamine                                                                       water white    2.15                         = 143 g. non-volatile                                                                        2.0 moles          transparent                                 = 3 equivalents                                                          8    85 g. UFM of Example 1                                                                       146 g. triethylene tetramine                                                                     light yellow   2.4                          = 47.5 g. non-volatile                                                                       1.0 mole           transparent                                 = 1 equivalent                                                           9    167 g. UFM of Example 1                                                                      486 g. 70% solution of                                                                           water white transparent;                                                                     about 1                      = 92 g. non-volatile                                                                         hexamethylene diamine in H.sub.2 O                                                               when cooled to 15° C., some          = 1.93 equivalents                                                                           = 340 g. non-volatile                                                                            white crystals formed but                                  = 2.93 moles       melted at 25° C.                10   260 g. UFM of Example 1                                                                      500 g. 70% solution of                                                                           water white    3.4                          = 144 g. non-volatile                                                                        hexamethylene diamine in H.sub.2 O                                                               transparent                                 = 3.04 equivalents                                                                           = 350 g. non-volatile                                                         = 3.20 moles                                              11   170 g. UFM of Example 1 = 95 g. non-volatile = 2.0                                            ##STR24##         water white transparent                                                                      1.8                       12 85 g. UFM of Example 1                                                                       230 g. Jeffamine D-230                                                                           very slightly yellow                                                                         3.3                          = 47.5 g. non-volatile                                                                       polyoxypropylene diamine                                                                         transparent                                 = 1 equivalent MW 230                                                    13   170 g. UFM of Example 1                                                                      122 g. monoethanol amine                                                                         light yellow   11.2                         = 95 g. non-volatile                                                                         = 2 moles          transparent                                 = 2 equivalents                                                          14   200 g. UPFM of Example 3                                                                     164 g. 85% solution of                                                                           light yellow   about 1.5                    urea-nonyl phenol                                                                            hexamethylene diamine in H.sub.2 O                                                               transparent                                 formaldehyde monomer                                                                         = 140 g. non-volatile                                          = 94 g. non-volatile                                                                         = 1.2 moles                                                    = 1.2 equivalents                                                        15   160 g. UPFM of Example 3                                                                     160 g. Adogen 572  light tan-yellow                                                                             1.1                          = 77 g. non-volatile                                                                         (oleyl diamine)    translucent                                 = 1.0 equivalent                                                                             = 1.0 equivalent                                          16   300 g. UPFM of Example 4                                                                     300 g. 70% solution of                                                                           light yellow   about 1.5                    = 150 g. non-volatile                                                                        hexamethylene diamine in H.sub.2 O                                                               transparent                            17   65 g. UFM of Example 1 = 36 g. non-volatile = 0.75                                            ##STR25##         water-white sl. cloudy                                                                       10.8                      18 43 g. UFM of Example 1                                                                       300 g. Jeffamine ED-600                                                                          water-white    11                           = 24 g. non-volatile                                                                         [poly(oxyethylene)diamine]                                                                       transparent                                 = 0.5 equivalent                                                                             mol. wt. 600                                              19   172 g. UFM of Example 1                                                                      340 g. isophorone diamine                                                                        water-white    33                           = 95 g. non-volatile                                                                         = two moles        transparent                                 = 2 equivalents                                                                              a product of Huels,                                                           formerly Veba                                             20   172 g. UFM of Example 1                                                                      316 g. trimethyl   very light yellow                                                                            3.8                          = 95 g. non-volatile                                                                         hexamethylene diamine                                                                            transparent                                 = 2 equivalents                                                                              = two moles                                                                   a product of Huels                                                            formerly Veba                                             21   85 g. UFM of Example 1                                                                       129 g. Naminoethyl piperazine                                                                    water-white    3.15                         = 47.5 g. non-volatile                                                                       = one mole         transparent                                 = 1.0 equivalent                                                         22   130 g. UFM of Example 1                                                                      171 g. of water white distillate                                                                 water-white    3.0                          = 71 g. non-volatile                                                                         prepared from du Pont DACH, a                                                                    transparent                                 = 1.5 equivalents                                                                            mixture of about half                                                         1,2,diamine cyclohexane, about                                                one-quarter hexamethylene diamine,                                            and remainder of related compounds                                            including 1,5 aminomethyl pentane                                             diamine. The original material is                                             very dark, but the distillate is                                              water white.                                              23   107 g. thiourea-formaldehyde                                                                 166 g. 70% hexamethylene diamine                                                                 water-white    4.0                          monomer in methanol,                                                                         in water           transparent                                 Example 2      = 116 g. 100% HMD                                              = 51.5 g. non-volatiles                                                                      =  1.0 mole                                                    = 1.0 equivalent                                                         24   85 g. UFM      136 g. m-xylene diamine                                                                          water-white    --                           = 47.5 g. non-volatile                                                                       = 1 mole           transparent                                 = 1 equivalent                                                           __________________________________________________________________________

EXAMPLES OF CURE OF EPOXY RESINS

The various urea-formaldehyde type polyamines were reacted with thestandard epoxy resin--the diglycidyl ether of bisphenol A.

The curing reactions were all begun at room temperature, with theresulting exotherm uncontrolled.

The polyamine-to-epoxy-resin ratios shown in the examples below are onlyapproximately stoichiometric and illustrate the curing ability of thesenew curing agents. For optimum results, one should vary the illustratedratios in each instance and study the properties of the resulting filmsor castings, to arrive at the desired property or properties, or toachieve a desired compromise. These properties may be hardness,flexibility, chemical resistance, etc., obtaining either a maximum ofone of these or the desired best overall aggregation of properties, formaximum results for one property does not necessarily mean maximumresults for another property; so there may not be any one ratio at whichthe best results for all properties coincide.

                                      TABLE II                                    __________________________________________________________________________    Example                                                                            UF Polyamine                Epoxy Curing                                                                             Properties of                     No.  Per Example                                                                             Reactants and Proportions                                                                       Results    Cured Resin                       __________________________________________________________________________    25   diethylene                                                                              30 g. - liquid epoxy resin,                                                                     Clear transparent                                                                        Film on steel                          triamine  Dow DER 331       mix at once.                                                                             very tough                             Example 6 13 g. - curing agent of Example 6                                                               Exothermed very hot                                                           in 40 minutes.                               26   diethylene                                                                              Same as 25 above  Same as 25 above                                                                         Same as 25 above,                      triamine                               but perhaps harder                     Example 7                              film                              27   triethylene                                                                             50 g. DER 331     Slightly cloudy                                                                          Very tough film                        tetramine 10 g. curing agent of Example 8                                                                 mix at once.                                      Example 8                   Exotherm hot in                                                               40 minutes                                   28   hexamethylene                                                                           30 g. DER 331     Very transparent                                  diamine   10 g. of curing agent of                                                                    15° C.                                                                     mix at once.                                      Example 9 Example 9 amine   Exotherm very, very                                                           hot in 45 minutes.                           29   hexamethylene                                                                           Same as 28 above  Same as 28 above                                  diamine                                                                       Example 10                                                               30   polyoxypropylene                                                                        30 g. DER 331     Clear transparent                                                                        Excellent, transparent                 diamine MW 400                                                                          15 g. curing agent of Example 11                                                                mix. Mild exotherm                                                                       tough, fairly flexible,                Example 11                  in about 4 hours.                                                                        glossy film.                      31   polyoxypropylene                                                                        30 g. DER 331,    Transparent mix.                                  diamine MW 230                                                                          15 g. curing agent of Example 12                                                                Slow but positive                                 Example 12                  cure at room                                                                  temperature.                                 32   monoethanol amine                                                                       30 g. DER 331,    Hazy mix, cured                                                                          Soft solid.                            Example 13                                                                              15 g. of curing agent of Example 13                                                             in 24 hours.                                 33   hexamethylene                                                                           30 g. DER 331,    Very hot exotherm                                                                        Excellent film                         diamne    15 g. of curing agent of Example 14                                                             in 40 minutes                                                                            on steel.                              Example 14                                                               34   oleyl diamine                                                                           30 g. DER 331,    Made transparent mix                              Example 15                                                                              30 g. of curing agent of Example 15                                                             at once. Mix applied                                                          to steel panel under                                                          water. Film cured                                                             under water in 24                                                             hours.                                       35   hexamethylene                                                                           53 g. DER 331     Mix transparent at                                                                       In 24 hours the                        diamine   18 g. of curing                                                                             15° C.                                                                     once. Very hot                                                                           film was glossy,                       Example 16                                                                              agent of Example 16                                                                             exotherm in 35                                                                           transparent and                                                    minutes. Applied to                                                                      very tough and                                                     steel panel. Set to                                                                      hard.                                                              solid film in 2 hours.                       36   polyoxypropylene                                                                        15 g. DER 331,                                                      triamine MW 400                                                                         30 g. of curing agent of                                                                    18° C.                                         Example 17                                                                              Example 17                                                     37   poly (oxyethylene)                                                                      30 g. DER 331,    Very transparent                                                                         Very slow cure.                        diamine MW 600                                                                          20 g. of curing agent of Example 18                                                             water-white mix                                                                          Formed a soft                          Example 18                  at once    casting in 10 days                38   isophorone                                                                              50 g. DER 331,    Made transparent                                  diamine   20 g. of curing agent of Example 19                                                             mix at once.                                      Example 19                  Water-white.                                                                  Hot exotherm in                                                               60 minutes                                   39   trimethyl 50 g. DER 331,    Made transparent                                  hexamethylene                                                                           20 g. of curing agent of Example 20                                                             mix at once.                                      diamine                     Exotherm of 70° C.                         Example 20                  in 90 minutes.                               40   N--amino ethyl                                                                          60 g. DER 331,    Made transparent                                                                         Made hard film on                      piperazine                                                                              30 g. of curing agent of Example 21                                                             mix at once. Very                                                                        an aluminum panel.                     Example 21                  hot exotherm in                                                               40 minutes.                                  41   1,2 diamine                                                                             30 g. DER 331,    Made transparent                                                                         Made hard film on                      cyclohexane                                                                             15 g. of curing agent of Example 22                                                             mix at once.                                                                             an aluminum panel.                     Example 22                  Hot exotherm in                                                               40 minutes                                   42   2,4 bis   20 g. DER 331,    Transparent dark                                                                         Made excellent hard                    (p-aminobenzyl)                                                                         10 g. of curing agent of Example 5                                                              brown-red liquid on                                                                      transparent glossy                     aniline   5 g. benzyl alcohol                                                                             mixing, cured to                                                                         adhesive film on                       Example 5                   hard casting in                                                                          steel and on aluminum                                              24 hours.  in 24 hours.                      43   hexamethylene                                                                           50 g. DER 331     Mix transparent                                   diamine   20 g. of curing agent of Example 23                                                             at once. Hot                                      Example 23                  exotherm in                                                                   35 minutes.                                  44   m-xylene  50 g. DER 331,    Mix transparent                                   diamine   20 g. of curing agent of Example 24                                                             at once. Hot                                      Example 24                  exotherm in                                                                   35 minutes.                                  __________________________________________________________________________

The invention having been described and exemplified what I claim as myinvention is:
 1. The reaction product of epoxy resin with ##STR26##where X¹ is ##STR27## and X² is X¹ or ##STR28## where R¹ is one of thefollowing: ##STR29## x varying from about 2 to about 6 ##STR30## wherex+y+z=about 5.3 ##STR31## where a+c=3.5 and b=13.5 ##STR32## R² and R³are both H where R¹ is any of (a) to (l) and when R¹ is (o), either R²or R³, but not both, is C₁₈ H₃₅, while the other is H, andR⁴ is H or analkyl radical with one to nine carbon atoms.
 2. The reaction product ofdiglycidyl ether of bisphenol A with ##STR33## where X is ##STR34##where R¹ is one of the following: ##STR35## x varying from about 2 toabout 6 ##STR36## where x+y+z=about 5.3 ##STR37## where a+c=3.5 andb=13.5 ##STR38## and R² and R³ are both H.
 3. The reaction product ofdiglycidyl ether of bisphenol A with ##STR39## where X¹ is ##STR40## andX² is ##STR41## where R¹ is one of the following: ##STR42## x varyingfrom about 2 to about 6 ##STR43## where x+y+z=about 5.3 ##STR44## wherea+c=3.5 and b=13.5 ##STR45## R² and R³ are both H, and R⁴ is H or analkyl radical with one to nine carbon atoms.
 4. The reaction product ofdiglycidyl ether of bisphenol A with ##STR46## where X¹ is ##STR47## andX² is X¹ or ##STR48## where R¹ is --CH₂ --CH₂ --CH₂ --, either R² or R³,but not both, being C₁₈ H₃₅, while the other is H, andR⁴ is H or analkyl radical with one to nine carbon atoms.
 5. The reaction product ofdiglycidyl ether of bisphenol A with ##STR49## where R¹ is ##STR50## 6.The reaction product of diglycidyl ether of bisphenol A with ##STR51##where R¹ is ##STR52##
 7. The reaction product of diglycidyl ether ofbisphenol A with ##STR53## where R¹ is --CH₂ --CH₂ --CH₂ --CH₂ --CH₂--CH₂ --.
 8. The reaction product of diglycidyl ether of bisphenol Awith ##STR54## where R¹ is ##STR55## x varying from about 2 to about 6.9. The reaction product of diglycidyl ether of bisphenol A with##STR56## where R¹ is ##STR57## where x+y+z=about 5.3.
 10. The reactionproduct of diglycidyl ether of bisphenol A with ##STR58## where R¹ is##STR59## where a+c=3.5 and b=13.5.
 11. The reaction product ofdiglycidyl ether of bisphenol A with ##STR60## where R¹ is ##STR61## 12.The reaction product of diglycidyl ether of bisphenol A with ##STR62##where R¹ is ##STR63##
 13. The reaction product of diglycidyl ether ofbisphenol A with ##STR64## where R¹ is ##STR65##
 14. The reactionproduct of diglycidyl ether of bisphenol A with ##STR66## where R¹ is##STR67##
 15. The reaction product of diglycidyl ether of bisphenol Awith ##STR68## where R¹ is ##STR69##
 16. The reaction product ofdiglycidyl ether of bisphenol A with ##STR70## where R¹ is ##STR71## 17.The reaction product of diglycidyl ether of bisphenol A with ##STR72##where R¹ is ##STR73##
 18. The reaction product of diglycidyl ether ofbisphenol A with ##STR74## where R¹ is a mixture of ##STR75##
 19. Acured epoxy resin comprising the reaction product of diglycidyl ether ofbisphenol A with the reaction product of about four moles of analiphatic, cycloaliphatic, or aromatic polyamine with about one mole ofa monomer of (a) urea-formaldehyde ether, (b) phenolic substitutedurea-formaldehyde ether, or (c) thiourea-formaldehyde ether, in whichthe ether group of the ether molecule is split and a carbon-nitrogenbond to an amine group is formed at the site of the ether splitting. 20.A cured epoxy resin comprising the reaction product of diglycidyl etherof bisphenol A with the reaction product of about four moles of analiphatic polyamine with one mole of a monomer of (a) urea-formaldehydeether, (b) phenolic substituted urea-formaldehyde ether, or (c) thioureaformaldehyde ether, in which the ether group of the ether molecule issplit and a carbon-nitrogen bond to an amine group is formed at the siteof the ether splitting.
 21. A cured epoxy resin comprising the reactionproduct of diglycidyl ether of bisphenol A with the reaction product ofabout four moles of a cycloaliphatic polyamine with one mole of amonomer of (a) urea-formaldehyde ether (b) phenolic substitutedurea-formaldehyde ether, or (c) thiourea formaldehyde ether, in whichthe ether group of the ether molecule is split and a carbon-nitrogenbond to an amine group is formed at the site of the ether splitting. 22.A cured epoxy resin comprising the reaction product of diglycidyl etherof bisphenol A with the reaction product of about four moles of anaromatic polyamine with one mole of urea-formaldehyde ether monomer, inwhich the ether group of the ether molecule is split and acarbon-nitrogen bond to an amine group is formed at the site of theether splitting.
 23. A method of curing epoxy resins, comprisingreacting an uncured epoxy resin at ambient temperature with ##STR76##where X¹ is ##STR77## and X² is X¹ or ##STR78## where R¹ is one of thefollowing: ##STR79## x varying from about 2 to about 6 ##STR80## wherex+y+z=about 5.3 ##STR81## where a+c=3.5 and b=13.5 ##STR82## R² and R³are both H where R¹ is any of (a) to (l) and when R¹ is (m), either R²or R³, but not both, is C₁₈ H₃₅, while the other is H, andR⁴ is H or analkyl radical with one to nine carbon atoms.
 24. A method of curingepoxy resins, comprising reacting uncured diglycidyl ether of bisphenolA with ##STR83## where X is ##STR84## where R¹ is one of the following:##STR85## x varying from about 2 to about 6 ##STR86## where x+y+z=about5.3 ##STR87## where a+c=3.5 and b=13.5 ##STR88## and R² and R³ are bothH.
 25. A method of curing epoxy resins, comprising reacting uncureddiglycidyl ether of bisphenol A with ##STR89## where X¹ is ##STR90## andX² is ##STR91## where R¹ is one of the following: ##STR92## x varyingfrom about 2 to about 6 ##STR93## where x+y+z=about 5.3 ##STR94## wherea+c=3.5 and b=13.5 ##STR95## R² and R³ are both H, and R⁴ is H or analkyl radical with one to nine carbon atoms.
 26. A method of curingepoxy resin, comprising reacting uncured diglycidyl ether of bisphenol Awith ##STR96## where X¹ is ##STR97## and X² is X¹ or ##STR98## where R¹--CH₂ --CH₂ --CH₂ -- either R² or R³, but not both, being C₁₈ H₃₅, whilethe other is H, andR⁴ is H or an alkyl radical with one to nine carbonatoms.
 27. A method of curing epoxy resin, comprising reacting uncureddiglycidyl ether of bisphenol A with ##STR99## where R¹ is ##STR100##28. A method of curing epoxy resin, comprising reacting uncureddiglycidyl ether of bisphenol A with ##STR101## where R¹ is ##STR102##29. A method of curing epoxy resin, comprising reacting uncureddiglycidyl ether of bisphenol A with ##STR103## where R¹ is --CH₂ --CH₂--CH₂ --CH₂ --CH₂ --CH₂ --.
 30. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR104## where R¹ is ##STR105## x varying from about 2 to about
 6. 31.A method of curing epoxy resin, comprising reacting uncured diglycidylether of bisphenol A with ##STR106## where R¹ is ##STR107## wherex+y+z=about 5.3.
 32. A method of curing epoxy resin, comprising reactinguncured diglycidyl ether of bisphenol A with ##STR108## where R¹ is##STR109## where a+c=3.5 and b=13.5.
 33. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR110## where R¹ is ##STR111##
 34. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR112## where R¹ is ##STR113##
 35. A method of curing epoxy resin,,comprising reacting uncured diglycidyl ether of bisphenol A with##STR114## where R¹ is ##STR115##
 36. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR116## where R¹ is ##STR117##
 37. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR118## where R¹ is ##STR119##
 38. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR120## where R¹ is ##STR121##
 39. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR122## where R¹ is ##STR123##
 40. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with##STR124## where R¹ is a mixture of ##STR125##
 41. A method of curingepoxy resin, comprising reacting uncured diglycidyl ether of bisphenol Awith the reaction product of about four moles of an aliphatic,cycloaliphatic, or aromatic polyamine with one mole of a monomer of (a)urea-formaldehyde ether, (b) a phenolic substituted monomer ofurea-formaldehyde ether, or (c) a monomer of thiourea-formaldehydeether, in which the ether group of the ether molecule is split and acarbon-nitrogen bond to an amine group is formed at the site of theether splitting.
 42. A method of curing epoxy resin, comprising reactinguncured diglycidyl ether of bisphenol A with the reaction product ofabout four moles of an aliphatic polyamine with one mole of a monomer of(a) urea-formaldehyde ether, (b) phenolic substituted urea-formaldehydeether, or (c) thiourea-formaldehyde ether, in which the ether group ofthe ether molecule is split and a carbon-nitrogen bond to an amine groupis formed at the site of the ether splitting.
 43. A method of curingepoxy resin, comprising reacting uncured diglycidyl ether of bisphenol Awith the reaction product of about four moles of a cycloaliphaticpolyamine with one mole of a monomer of (a) urea-formaldehyde ether, (b)phenolic substituted urea-formaldehyde ether, or (c)thiourea-formaldehyde ether, in which the ether group of the ethermolecule is split and a carbon-nitrogen bond to an amine group is formedat the site of the ether splitting.
 44. A method of curing epoxy resin,comprising reacting uncured diglycidyl ether of bisphenol A with thereaction product of about four moles of an aromatic polyamine with onemole of a urea-formaldehyde ether monomer, in which the ether group ofthe ether molecule is split and a carbon-nitrogen bond to an amine groupis formed at the site of the ether splitting.
 45. The reaction productof the composition of claim 1 with diglycidyl ether of bisphenol A. 46.The reaction product of (1) the reaction product obtained by reactingabout four moles of monoethanol amine with one mole of a monomer ofurea-formaldehyde ether, to split the ether group of saidurea-formaldehyde ether molecule and form a carbon-nitrogen bond to anamine group at the site of the ether splitting, with (2) diglycidylether of bisphenol A.
 47. A method for curing epoxy resin comprising thesteps of:(a) reacting urea and paraformaldehyde in a lower alcohol underbasic conditions and under heat well below boiling of the alcohol andwell above room temperature, (b) adding acid to make the reactionstsrongly acidic, with resulting exotherm, (c) holding the reaction atabout 70°-120° C. for about an hour, and (d) bringing the pH to about7.0, (e) removing the resulting urea-formaldehyde ether monomer from theremaining material, (f) reacting one mole of the urea-formaldehyde ethermonomer with about four moles of monoethanol amine to split the ethergroup of the urea-formaldehyde ether molecule and form a carbon-nitrogenbond to an amine group at the site of the ether splitting, (g) reactingthe product resulting from step (f) with uncured diglycidyl either ofbisphenol A.